Basic nitrogen polycondensates and dyereceptive polyolefin compositions containing such polycondensates



United States Patent 3,510,437 BASIC NITROGEN POLYCONDENSATES AND DYE-RECEPTIVE POLYOLEFIN COMPOSITIONS CON- TAINING SUCH POLYCONDENSATESAlberto Bonvicini and Giuseppe Cantatore, Terni, Italy, assignors toMontecatini Edison S.p.A., Milan, Italy, a corporation of Italy NoDrawing. Filed May 22, 1967, Ser. No. 640,336 Claims priority,application Italy, May 27, 1966, 12,363/ 66 Int. Cl. C03d 33/06 US. Cl.260-2 2 Claims ABSTRACT OF THE DISCLOSURE New basic polycondensatesobtained by reacting the condensation product of epichlorohydrin and aheterocyclic seven-membered dise-condary diamine, this condensationproduct having the formula:

wherein R radicals are the same or different radicals selected from thegroup consisting of hydrogen and alkyl radicals having 1-12 carbonatoms, and n is an integer from 1 through 100, with a polyaminecontaining primary amino groups of the type RHN...X...NH

where R is H, an alkyl group or a residue of a heterocyclic nucleus andX is a residue of a bivalent hydrocarbon, optionally containing S, N, O,etc., for example, hexamethylenediamine, ethylenediamine,diethylenetriamine, tetraethylenepentamine, aminoethylpiperazine N-methylhexamethylenediamine, N-isopropylhexamethylenediamine,3,3-diaminodipropylether, 3,3'-diaminodiphenylmethane,N,N'-bis-(3-amino-propyl)piperazine, and the like.

Dye-receptive compositions, preferably in the form of textile fibers,comprising 1-25% by weight of the above polycondensate and,correspondingly, 99-75% by Weight of a synthetic polymer, e.g., apolyolefin.

BACKGROUND OF THE INVENTION Field of the invention The present inventionrelates to new basic polycondensates obtained by forming a condensationproduct of epichlorohydrin with a heterocyclic seven-membereddisecondary diamine and then reacting the resulting condensation productwith a polyamine containing primary amino groups. The present inventionalso relates to dyereceptive compositions, which can be used to formtextile fibers (as well as films, ribbons, shaped articles and thelike), which compositions are particularly receptive towards thedyestuffs which are generally used in the dyeing of wool.

3,5 10,43 7 Patented May 5, 1970 ice Description of the prior artSUMMARY OF THE INVENTION The present invention provides new basicnitrogen polycondensates and dye-receptive compositions havingparticular receptivity to wool dyestuffs comprising polyolefins havingthese new polycondensates admixed therewith. Thus, we have surprisinglyfound that textile fibers having a particular aflinity for dyestuffs areobtained by extruding the dye-receptive compositions of the presentinvention, which compositions are mixtures of high molecular weightpolymers with 1-25% by weight of the mixture of the basic nitrogenpolycondensates of the present invention.

More particularly, the basic nitrogen polycondensates of the presentinvention are the reaction products obtained by 1) condensation ofepichlorohydrin with a heterocyclic seven-membered disecondary diaminehaving the formula:

H R R 154%,, Mi; u R R- 2 a ile R wherein the R radicals are the same ordifferent radicals selected from the group consisting of hydrogen andalkyl radicals preferably having 1-12 carbon atoms, so as to obtain acondensation product having the formula:

wherein R is as defined above and n is an integer from 1 through and (2)reacting this condensation product with a polyamine containing primaryamino groups of the type RHN....X...NH

where R is H, an alkyl group or a residue of a heterocyclic nucleus andX is a residue of a bivalent hydrocarbon, optionally containing S, N, 0etc., this polyamine being selected from the group consisting ofhexamethylenediamine, ethylenediamine, diethylenetriamine,tetraethylenepentamine, aminoethylpiperazine,N-methylhexamethylenediamine, N isopropylhexamethylenediamine,3,3-diaminodipropylether, 3,3'-diaminodiphenylmethane, andN,N'-bis-(3-aminopropyl)piperazine; the molar ratios ofepichlorohydrin/heterocyclic diamine/polyamine being within the range of1/0.5-O.99/0.01-1.

The representative structural formula for the entire 3- componentpolycondensate may be specified as follows:

The polycondensates of the present invention contain the followingstructural units:

R R R R 1 l --CHzOHCHaN N-CHCHCHz-N-XNH H R l R H I R V R R n 111wherein m and n are integers from l to 100.

The dye-receptive composltions of the present invention comprise fromabout 1-25 by weight of the basic nitro- 0H gen polycondensate of thepresent invention and, corre- R R spondingly, from about 99-75% byweight of a crystalline polymer of an olefin having the formula RCH=CH Qwherein R is selected from the group consisting of hydrogen, alkylradicals and aryl radicals having 1 to 12 C g atoms. R

The dye-receptive fibers of the present invention may be obtained byextrusion of the dye-receptive compositions Wh?rem R 15 as defined aboveand resldues of the P l" of the present invention. amldes used Thepresent invention provldes certaln economical ad- DESCRIPTI OF THEPREFERRED vantages, in that the cost of the modifier agents used andEMBOD 1 of the starting materials necessary for their synthesis is Thepreferred synthetic polymers for use in the comlow, as eelhpafed to thatfor the Prior art ifie spositions of the present invention arepolyolefins having The mlXlhg 9 the haste nitrogen polycondensates Withprevailingly isotactic structure, obtained by polymerizathe Polyolefin15 generally Carried out y p y mixing tion under low pressure, withstereospecific catalysts. the polyeehelehsete With the P y underagitation. More preferably, polypropylene consisting essentially ofHowever, it 13 p h e to Carry out the addition y other isotacticmacromolecules is used. Other polymers suitable methods Such as mlxhlgthe Polyelefin With Solution of for use in the compositions of thepresent invention inthe pelyeohdehsate In a Sultahle Solvent, followed yclude the crystalline polyolefins obtained from monomers evaporatloh ofthe Solvent itself, y addition of the having the formula R cH:cH,,wherein R is an alkyl pe e e to the pelyelefin at the end of the p y oraryl group having 1 to 12 C atoms or a hydrogen erization. It is furtherpossible to apply the polycondenatom, polyethylene, p01ybutene4,polypentene4, sate to the manufactured articles, for instance byimmerspolyhexeneq, 1 4 h 1 1 polyoctene4, l mg the artlcles in asolution or dispersion of the polyconstyrene etc. In addition to theolefin polymers, polymers dehsete and then evaporating the SOh/eht- Theapplication of different monomers, including acrylic, vinyl and similaryh made before after the stretching of the fibers, polymers, e.g.,acrylom'trile polymers, vinyl chloride polyfor times of from a fewseconds to several hours, at temmers, etc. may be modified with thepolycondensates of PeretufeS Y y h from room temperature to below thepresent invention to form dye-receptive compositions the eoftehlhg Polhtt the p y suitable for use in preparing dye-receptive fibers, etc. e y,the mlxtures are granulated and then Suitable heterocyclic disecondarydiamines for use in truded Wlth melt spihhihg devices through eifeulel Pprepar'ing the p01ycondensatesinc1ude; nerets preferably havinglength/diameter ratios higher than 1, or through non-circularspinnerets. 5s7'mmethylhomoplpemzme' The granulation and the spinning ofthe mixes are pref- 2- erably carried out by working in the absence ofoxygen, NH R under an atmosphere of an inert gas, e.g., nitrogen. The lspinning of the mixes may be also carried out in the HEFCHQiOHrCwHQtpresence of a small amount of a solid dispersing agent,5,6,7'tf1methl1hmP1Perallhe3 for example, cetyl alcohol, stearic acid,stearamide, N-

CH2OH2 dihydroxyethyl-lauramide, and the like. NH NH During the mixing,in addition to the polycondensates E 1 of the present invention,opacifiers (such as TiO CaCO- H CH3) CH(OH3)- men) ZnO), organic andinorganic stabilizers (such as lauryl- 5,7-dimethylhomopiperazine:thio-dipropionate, trisnonylphosphite, calcium stearate, ZnS) and dyeingpigments (such as Cadmium Yellow, NH E Cl. 37; Chromoftal BR, Cl. 144;Nylofile BLL, 0.1.

| I 15) may also be added to the polymers. ECW119431? Hwm) 5 The fibers,after spinning, may be subjected to a stretch-5,6-dimethyl-7-propylhomopiperazine2 ing process, with stretching ratiosbetween about 1:2 and 1 CH CH 1:10, at temperatures of about 80150 C.,in drawing devices heated with warm air, or steam, or with a similar NENH fluid, or provided with a heating plate. It is then possible B J; tosubject the fibers to dimensional stabilization, under 0 H free orprevented shrinking conditions, at about a 7 C.tetramethylhomopiperazine and similar compounds. The The fibers obtainedby extrusion of the mixes of the synthesis of these compounds has beendescribed, e.g., in present invention can be mono or plurifilaments andmay US. patent application Ser. No. 591,687. 75 be used for thepreparation of continuous thread or staple,

or for the preparation of bulk yarns or bulk staples. The mono andplurifilaments prepared according to the present invention may, ifnecessary, be treated with reactants capable of rendering the nitrogenpolycondensates present in the manufactured article completelywater-insoluble. Particularly suitable for this treatment are mono anddiepoxy compounds (such as ethylene oxide,ethyleneglycoldiglycidylether), mono and diisocyanates (such aphenylisocyanates and 2,4-toluylene diisocyanate), mono and dialdehydes(such as formaldehyde, glyoxal), halogens, metal salts, and the like.These treatments are described, e.g., in British Pat. 942,131 and982,953, and may be carried out before or after stretching.

The fibers obtained in accordance with the present invention have aremarkable receptivity towards the acid, metallized and plastosolubledyestuffs. The dyed fibers also exhibit an increased stability,particularly to light.

The compositions according to the present invention can also be used forthe preparation of films, ribbons, shaped articles and the like. Thefibers and the other manufactured articles can also be subjected to anacid treatment which further improves the dyeability and the fastness ofthe dyeings (for instance according to U.S. Pat. 3,151,928).

The dyeings were carried out for an hour and a half at the boilingpoint, in dyebaths containing 2.5% of dyestuff (plastosoluble, acid ormetallized dyestuff) by weight of the fiber, with a fiber/dyebath ratioof 1:40. The dyeings with acid and metallized dyestuffs were carried outin the presence of 1% by weight of the fiber of a surfactant consistingof the condensation product of ethylene-oxide and an alkyl phenol suchas Aionico SCL of Soc. Chimica Lombarda A.E. Bianchi, Rho (Milan) Italyor sodium alkylbenzenesulfonates such as Dispergal SCLG ofMontecatini-Edison or the sodium salt of N- oleyl-N-methyltaurine. 30minutes after the beginning of the boiling, 2% by weight of the fiber ofa 20% acidic acid solution was added in order to improve the dyebathexhaustion. The dyeings with plastosoluble dyestuffs were carried out inthe presence of 2% of the surfactant by the weight of the fiber.

After dyeing, the fibers were rinsed with running water, and wereintensely dyed. The fastness of the dyeings to light, washing, cleaningwith trichloroethylene and t0 rubbing were completely satisfactory.

The following examples are presented to further illustrate the inventionwithout limiting its scope.

EXAMPLE 1 Into a one liter 3-necked flask, provided with a stirrer,thermometer and reflux condenser, there were introduced 142.2 g. (1 mol)of 5,5,7-trimethylhomopiperazine, 101.75 g. (1.1 mols) ofepichlorohydrin and 230 cc. of isopropyl alcohol.

The mixture was refluxed for hours. During the last 8 hours of reflux 36g. NaOH were added. Thereafter, a solution of 17.4 g. (0.15 mol) ofhexamethylenediamine in 50 cc. of isopropyl alcohol was added and theresulting mixture refluxed for an additional 6 hours. During the last 2hours of refluxing, 9.3 g. of NaOH were added. After an additional 4hours of refluxing, the reaction mixture' was filtered to separatesodium chloride and the solvent then removed by distillation underreduced pressure (ll0l20 C. under a residual pressure of 2-3 mm. Hg).

The resinous material thus obtained, after drying, had a light yellowshade, was brittle, and was slightly soluble in water.

The percent nitrogen found was lated: 14.55

40 g. of the polycondensate thus obtained (ground into a fine powder)were mixed with 0.956 kg. of polypropylene, 3 g. of calcium stearate and1 g. of TiO at room temperature in a Henschel mixer.

The polypropylene used had the following characteristics: ['r ]=1.54(determined in tetrahydronaphthalene at 14.2 (calcu- 135 C.); ashcontent=0.0l2%; residue after the heptane extraction=97.2%

The resulting mixture was granulated in an extruder under an oxygen-freeatmosphere at 220 C.

The granulate obtained was spun with a laboratory melt spinning deviceunder the following conditions:

spinning temperature:250 C. spinneret type=10/ 0.8 x 16 mm.

After stretching and treatment with a 3% aqueous solution ofethyleneglycol diglycidyl ether, followed by heating at 140 C. for 10minutes, the fiber had the following characteristics:

tenacity (g./den.):5.13 elongation (percent) :27.

The fibers were dyeable with acid, chrome, metallized and plastosolubledyestuffs, including Brilliant Blue Alizarine Fallon BL (C.I. Acid BlueViolet Neolan, 5 RF (C.I. Acid Violet 58), Lanasyn Red 2 GL (C.I. AcidRed 216), Brown Lanasyn GRL, Yellow Supranol Fast 4 GL (C.I. Acid Yellow79).

EXAMPLE 2 Into a 1 liter, S-necked flask, provided with a stirrer,thermometer and reflux condenser, there were introduced 142.2 g. (1 mol)of 5,5,7-trimethylhomopiperazine, 101.75 g. (1.1 mols) ofepichlorohydrin and 230 cc. of isopropyl alcohol.

The mixture was refluxed for 10 hours, 36 g. of NaOH being added duringthe last 8 hours of reflux. Then a solution of 7.2 g. (0.12 mol) ofethylenediamine in 20 cc. of isopropyl alcohol was added and theresulting mixture refluxed for an additional 6 hours, 9.3 g. of NaOHbeing added during the last 2 hours of refluxing. After an additional 4hours of refluxing, the reaction mixture was filtered to separate sodiumchloride and the solvent then removed by distillation.

The resinous material thus obtained, after drying, had a light yellowcolor, and was brittle and slightly soluble in water. The percentnitrogen found was 14.5 (calculated=14.8%

40 g. of the polycondensate thus obtained (ground into a fine powder)were mixed with 0.95 6 kg. of polypropylene, 3 g. of calcium stearateand 1 g. of TiO at room temperature in a Henschel mixer.

The polypropylene used had the following characteristics:

[7 ]=1.54 (determined in tetrahydronaphthalene at C.) ash content=0.0l2%residue after the heptane extraction=97.2%.

The resulting mixture was granulated in an extruder under an oxygen-freeatmosphere at 220 C.

The granulate obtained was spun with a laboratory melt spinning deviceunder the following conditions:

spinning temperature=250 C. spinneret type=10/0.8 x 16 mm.

After stretching and treatment with a 3% aqueous solution ofethyleneglycol diglycidyl ether, followed by heating at C. for 10minutes, the fiber had the following characteristics:

tenacity g./ den.) =5.5 elongation (percent):26

The fibers were dyeable with acid, chrome, metallized, and plastosolubledyestuffs, including Brilliant Blue Alizarine Follon BL (Cl. Acid Blue80), Violet Neolan 5 RF (C.I. Acid Violet 58), Lanasyn Red 2 GL (C.I.Acid Red 216), Brown Lanasyn GRL, Yellow Supranol Fast 4 GL (C.I. AcidYellow 79).

EXAMPLE 3 Into a 1 liter, 3-necked flask, provided with a stirrer,thermometer and reflux condenser, there were introduced 142.2 g. (1 mol)of 5,5,7-trimethylhomopiperazine, 101.75 g. (1.1 mols) ofepichlorohydrin and 230 cc. of isopropyl alcohol.

The mixture was refluxed for 10 hours, 36 g. of NaOH being added duringthe last 8 hours. Then a solution of 12.36 g. (0.12 mol) ofdiethylenetriamine in 20 cc. of isopropyl alcohol was added and theresulting mixture refluxed for an additional 6 hours, 9.3 g. of NaOHbeing added during the last 2 hours. After an additional 4 hours ofrefluxing, the reaction mixture was filtered to separate sodiumchloride, and solvent then removed by distillation.

The resinous material thus obtained, after drying, had a light yellowcolor and was brittle and slightly soluble in water. The percentnitrogen found was 14.9 (calculated 15.2%

40 g. of the polycondensate thus obtained (ground into a fine powder)were mixed with 0.956 kg. of polypropylene, 3 g. of calcium stearate and1 g. of TiO at room temperature in a Henschel mixer.

The polypropylene used had the following characteristics:

[1 ]=1.54 (determined in tetrahydronaphthalene at 135 C.) ashcontent=-0.012% residue after heptane extraction=97.2%

The resulting mixture was granulated in an extruder under an oxygen-freeatmosphere at 220 C.

The granulate obtained was spun with a laboratory melt spinning deviceunder the following conditions:

spinning temperature=250 C. spinneret type=l/ 0.8 X 16 mm.

After stretching and treatment with 3% aqueous solution ofethyleneglycol diglycidyl ether, followed by heat ing at 140 C. for 10minutes, the fiber had the following characteristics tenacity g./ den.).4 elongation (percent) =28 The fibers were dyeable with acid, chrome,metallized and plastosoluble dyestuffs, including Brilliant BlueAlizarine Follon BL (C.I. Acid Blue 80), Violet Neolan 5 RF (C.I. AcidViolet 5 8), Lanasyn Red 2 GL (C.I. Acid Red 216), Brown Lanasyn GRL,Yellow Supranol Fast 4 GL (C.I. Acid Yellow 79).

EXAMPLE 4 Into a 1 liter, 3-necked flask, provided with a stirrer,thermometer and reflux condenser, there were introduced 142.2 g. (1'mol) of 5,5,7-trimethylhomopiperazine, 111 g. (1.2 mols) ofepichlorohydrin and 250 cc. of isopropyl alcohol.

The mixture was refluxed for 10 hours, 32 g. of NaOH being added duringthe last 8 hours. Then a solution of 27.8 g. (0.24 mol) ofhexamethylenediamine in 50 cc. of isopropyl alcohol was added and theresulting mixture was refluxed for an additional 6 hours, 17.5 g. ofNaOH being added during the last 2 hours. After an additional 4 hours ofrefluxing, the reaction mixture was filtered to separate sodium chlorideand the solvent then removed from the filtrate by evaporation underreduced pressure.

The resinous material thus obtained, after drying at 120 C. under 23 mm.Hg. vacuum, had a light yellow color and was brittle and slightlysoluble in water. The percent nitrogen found was 14.2 (calculated14.6%).

40 g. of the polycondensate thus obtained (ground into a fine powder)were mixed with 0.956 kg. of polypropylene, 3 g. of calcium stearate and1 g. of TiO at room temperature in a Henschel mixer.

The polypropylene used had the following characteristics:

[ ]=1.54 determined in tetrahydronaphthalene at 135 C.) ashcontent=0.012% residue after heptane extraction:97.2%

The resulting mixture was granulated in an extruder under an oxygen-freeatmosphere at 220 C.

The granulate obtained was spun with a laboratory melt spinning deviceunder the following conditions:

spinning temperature=250 C. spinneret type=10/ 0.8 x 16 mm.

After stretching and treatment with a 3% aqueous solution ofethyleneglycol diglycidyl ether, followed by heating at 140 C. for 10minutes, the fiber had the following characteristics:

tenacity (g./den.)=5.7 elongation (percent) :22

The fibers were dyeable with acid, chrome, metallized and plastosolubledyestuffs, including Brilliant Blue Alizarine Follon BL (C.I. Acid BlueViolet Neolan 5 RF (C.I. Acid Violet 58), Lanasyn Red 2 GL (C.I. AcidRed 216), Brown Lanasyn GRL, Yellow Supranol Fast 4 GL (C.I. Acid Yellow79).

EXAMPLE 5 Into a 1 liter, 3-necked flask, provided with a stirrer,thermometer and reflux condenser, there were introduced 156.2 g. (1 mol)of tetramethylhomopiperazine (obtained by hydrogenating 1,2propylenediamine and mesityloxide), 101.75 g. (1.1 mols) ofepichlorohydrin and 250 cc. of isopropyl alcohol.

The mixture was refluxed for 10 hours, 36 g. of NaOH being added duringthe last 8 hours. Then a solution of 12.36 g. (0.12 mol) ofdiethylenetriamine in 40 cc. of isopropyl alcohol was added and theresulting mixture was refluxed for an additional 6 hours, 9.3 g. of NaOHbeing added during the last 2 hours. After an additional 4 hours ofrefluxing, the reaction mixture was filtered to separate sodium chlorideand the solvent then removed from the filtrate by heating at -120 C.under reduced pressure.

The resinous material thus obtained, after drying, had a yellow colorand was brittle and slightly soluble in water. The percent nitrogenfound was 14.0 (calculated 14.3

42 g. of the polycondensate thus obtained (ground into a fine powder)were mixed with 0.954 kg. of polypropylene, 3 g. of calcium stearate and1 g. of TiO at room temperature in a Henschel mixer.

The polypropylene used had the following characteristics:

[1 ]=1.54 (determined in tetrahydronaphthalene at C.) ash content=0.012%residue after heptane extraction=97.2%.

The resulting mixture was granulated in an extruder under an oxygen-freeatmosphere at 220 C.

The granulate obtained was spun with a laboratory melt spinning deviceunder the following conditions:

spinning temperature=250 C. spinneret type=10/ 0.8 x 16 mm.

After stretching and treatment with a 3% aqueous solution ofethyleneglycol diglycidylether, followed by heating at C. for 10minutes, the fiber had the following characteristics:

tenacity (g./den.)=5.1 elongation (percent)=29 The fibers were dyeablewith acid, chrome, metallized and plastosoluble dyestufis, includingBrilliant Blue Alizarine Follon BL C. I. Acid Blue 80), Violet Neolan 5RF (C.I. Acid Violet 58), Lanasyn Red 2 GL (C.I. Acid Red 216), BrownLanasyn GRL, Yellow Supranol Fast 4 GL (C.I. Acid Yellow 79).

Variations and modifications can, of course, be made without departingfrom the spirit and scope of the invenion.

Having thus described the invention, what is desired to be secured byLetters Patent and is hereby claimed is:

1. A resinous basic nitrogen polycondensate consisting of the reactionproduct obtained by reacting a condensation product having the formula:

10 enediamine, 3,3 diaminodipropylether, 3,3 diaminodipheuylmethane, N,Nbis (3 aminopropyl)piperazine, and aminoethylpiperazine; the molarratios of epichloro hydrinzheterocyclic diamine:polyamine being withinthe approximate range of 1:0.5-0.99:0.0l1.

2. The polycondensate of claim 1 wherein said condensation product isprepared from the reaction of 5,5,7- trimethylhomopiperazine ortetramethylhomopiperazine with epichlorohydrin.

References Cited UNITED STATES PATENTS 2,849,411 8/1958 Lehmann et a1260-292 WILLIAM H. SHORT, Primary Examiner E. A. NIELSEN, AssistantExaminer US. Cl. X.R.

